Steam or



F 1). 7, 1956 J. F. NELSON ETTAL 2,734,046

PROCESS FOR PREPARING PETROLEUM RESINS Filed Oct. 1. 1952 C5 STEAM OR 1 STREAM rs T'mzi a m *5 I 05 souncm REMovAQ I 2 F L THERMAL 1y L.....I 7 SOAKER Y -J OYCLOPEN'IADIENE DIMER GONCENTRATE CATALYST 0 0 IO N (POLYMERIZATION LIQUID u POLYMER I CATALYST REMOVAL ATMOSPHERIC DIST'N. 19 STEAM OR m vAc. DISTN.

S M? 3 t 06G 8 p prt $077. RVER 0T8 United States Patent PROCESS FOR PREPARING PETROLEUM RESINS Joseph F. Nelson, Rahway, Robert F. Leary, Cranford, and Fred W. Banes, Westfield, N. 1., assignors to Esso Research and Engineering Company, a corporation of Delaware- Application October 1, 1952, Serial No. 312,466

scrum. (Cl. 260-82) This invention is concerned with the production of light colored resins from unsaturated petroleum fractions obtained by steam cracking and. more particularly, with the production of resins from a fraction substantially free of cyclic dienes by the use of an aluminum halide catalyst. The polymerization process also produces fractions having relatively aromatic content from which chemically pure components can be recovered.

Although petroleum fractions from cracking operations have previously been used for preparing resins, the improved methods of this patent employ streams having controlled compositions and also use critical conditions of polymerization to give high quality, light colored resins. and at the same time. yield by-product streams which are free of sludge forming components but conlain high concentrations of the desired aromatics.

The invention is of especial importance as a valuable process for the production of light colored resins from the highly unsaturated petroleum fractions produced by steam cracking of petroleum gas oil fractions or heavy naphthas. Preferably, the yclic. diolefins, such as cycloentadiene and methylcyclopeutadiene, are removed from a steam cracked fraction boiling largely below Cs.

These cyclic diolefins are preferably removed by dimerization and distillation. The overhead so obtained, chiefly a Cs-r fraction boiling below Cs or C9, is polymerized at an approximate temperature range of -40 to +70 C. with s alumin m alide atalyst. ithe as h li in a finely divided state, or as a slurry or in solution.

It is esp a ly ne s ry ha e re in produced be I light colored and preferably the. resins have high softens po n s- S cb resin ar of par ic l usefulness in preparing floor tile formulations, and the like.

Briefly, the broad concept of the invention includes the f ollowing steps.

Petroleum fractions such as keros n gas oil, naphtha,-

etc. are cracked in the presence of steam at temperatures of about 1000 F. to 1500'- F. to give highly unsaturated products. The liquid cut boiling largely below about Co is segregatedandheated-at about; 9010 140' C. to dimerize cyclopentadienes. Thereafter 0. Ce to Co and lighter liquid out including Cs is taken overhead and there is separated a dimer concentrate $8 bottoms. The overhead stream-thus largely freed of cyclodirliss, is the raw fo m eri r resinss stream is fl s th an halide catalyst at about -q0 t 7 9, under conditions of good ag tation. The resin thus formed may be recovered by water and/or alkali washing to remove catalyst followed, by stri ing oil the unpolvrnericed material- One sood way to remove the halide at. is to and methyl alcohol to form a solid complex, w ch is then filtered off.

Superior light amber colored resins can be made tn this way. These resins are well suited for making floor tile of the so-callcd asphalt type.

This invention pertains to a series of operations whereby the cracked distillate stream, boiling in the, range of about 20 to 140 C., is treated to remove certain cyclic dienes, such as cyclopentadiene, and the like by thermal soaking followed by distillation. If desired, some portion of the Cs fraction may be removed by distillation in a subsequent step although this is not necessary for th production of good resins. The unsaturated hydrocarbon mixture is polymerized with MC]: or AlBra and the resin is recovered from this polymerized reaction product. In general, from 0.25 up to 3.0%. of the catalyst gives quite satisfactory results.

The table below shows the ranges of composition which can be used as feed material for these resins.

The diolefin content of the mixture was obtained by reacting a mixture of 1.5 to 3.0 ml. of sample and 1.5 ml. of chloromnleic anhydride (diluted with 2 ml. benzene containing 0.1% tertiary butyl catechol) for 3 hours at C., and steam distilling the resulting reaction mixture for 2 hours to recover HCl (l mole/mole of diolefin).

The invention is described in more complete detail by the following examples and the accompanying figure, although it is not intended to limit the scope of the invention thereto.

EXAMPLE 1 A steam cracked distillate substantially all of which (95%) boiled between 25 and 135" C.. was held for 7 hours at a temperature of C. to dimerlze substantially all cyclodienes. A cut (25' C.-95 C.) had the following weight percent composition:

Percent Benzene 24.3 Diolefins 20.8 Parafllns (5.0 Olefins Remainder This material (19.8 parts by weight). was then agitated at 20' C. while. 5 parts of powdered A101: (30. mesh) was added over a period of 15 minutes. The agitation was continued for an additional 15 minutes, after which the reactor contents were washed with 5% NaOH and 3 times with water. After stripping at 7 mm. pressure to a 200' C. temperature at the bottom 73 parts'of a light colored resin was obtained. This resin was a hard product at room temperature, and had a ring and ball softening point of 93.5 C. and an iodine number (Wijs) of 80.2.

accompanying figure is presented. A steam cracked distillate boiling largely in the range of 25 to C. is

taken via line 1 to a thermal soaker wherein the cyclopentadienes are converted substantially completely to dimers. The thennal soaked product is taken by line 2 to the mid section of a distillation tower, operated under vacuum or with steam, to remove cyclodiene dimers as a concentrate stream 3 from the lower portion of the tower. The undimerized portion, C-C8, is passed overhead as stream 4 to a receiver and reflux drum where part is returned to the upper part of the fractionator by lines 5 and 6 as refiux. A portion can be removed from the system, if desired, by line 9. The undimerized portion, Cs-Ca, is passed by lines 8 and 10 to a polymerization zone. If desired, a part or all of stream 8 can be by-passed to a C5 removal zone and thereafter returned to the main stream by line 7 for polymerization. After addition of AlCls catalyst by inlet 13, the stream is subjected to polymerization at approximately room temperature. The polymerized reaction mixture 14 is passed through a catalyst re moval zone and thence as stream 15 to a distillation zone. From this distillation zone, a C5-C8 vapor stream 16 is removed and can be utilized for isolating aromatic components. 'A crude resin fraction 17 is passed to a distillation zone from which a liquid polymer stream 18 is removed overhead and the finished resin 19 is removed as bottoms product. The process may either be operated batchwise or in a continuous manner.

The resins produced as described above are amber colored products having softening points in the range of 70 to 105 C. and usually represent yields of 15 to 35% on the hydrocarbon feed. Examples of the preparation and properties of such resins are given in the examples and tables following.

EXAMPLE 3 The resins prepared with AICI: catalysts have numerous ,oints of superiority over those prepared with other Friedel-craft catalysts such as BFs. These points are well illustrated by the data of the following examples.

The hydrocarbon feed is a mixture of overhead fractions from cyclopentadiene recovery units boiling from 20 to 135 C. Both solid AlCla and gaseous BF: were employed as catalysts and the results in resin production were evaluated and compared. The AlCls reactions were worked up by adding 2.5% methyl alcohol to the reaction mixture, followed by filtration. The BF: reactions were worked up by adding isopropyl alcohol to the reaction mixture, followed by water washing. The reaction conditions and data obtained on the products are shown in Table I.

These data illustrate the advantages of MCI: catalysis to be (1) the production of a higher yieldof a. higher softening point resin, and (2) the production of resins having lower unsaturation. It is to be noted especially that only a small quantity of low boiling polymer product is produced with aluminum chloride whereas with BF:

this intermediate boiling material amounted to about 10% based on the feed.

The light color of these resins is also particularly desirable. They are generally of light or medium amber color and have Gardner colors of 2 to 3. The resin color is determined by direct comparison of the color produced by a 2 weight per cent solution of resin in xylenes with the Gardner color index.

TABLE I Comparison of polymerization catalysts PRODUCT RECOVERED AS RESIDUE FROM STRIPPING TO A BOTTOMS TEMP. 0]? 450 1?. ATM. PRESSURE Yield, Wt. Percent on Hydrocarbon Feed.

Vise. SSU 210 F Color, Gardner (diluted) Gram, API 60 F-.- Non-Volatile:

3 Hrs 24 Hrs Ash, Percent PRODUCT RECOVERED AS RESIDUE FROM STRIPIPING TO A BOTTOMS TEMP. OF 500 F. 2 MM. Hg

Yield, Wt. Percent on 22.5 13.9.

Hydrocarbon Feed.

Wt. Percent Liquid Poly- 8.8.

met on Feed.

Iodine No. 1%) 148.

Softening Point, C 7' 26-30.

PRODUCT RECOVERED AS RESIDUE AFTER STRIPPING 1 Wiis Iodine No. (5 ml. of 0.2 N Wiis reagent per 004-0055 g. of sample) EXAMPLE 4 Another advantage of AlCl: catalyzed polymerizations over BFs catalyzed polymerizations lies in the fact that theformer systems show less corrosivity in carbon steel equipment. This is illustrated by comparison of data given in Table II below. In obtaining these data, 1" x 2" strips of polished carbon steel sheeting, A thickness, were placed in the reactor along with the hydrocarbon charge. The indicated catalyst ,was added to eflfect polymerization. After completion of catalyst addition, the reaction mixture was held at F. for 48 hours after which the steel plates were'removed, washed thoroughly and weighed. The data indicate that in systems contammg varying amounts of water, the corrosivity of the BF: systems was severe whereas no corrosion occurred in the AlCls systems.

TABLE II Corrosion of carbon steel in polymerization systems Catalyst 0.75% BF: 1.0% AlCh Tem Time Wt. wt.

(Hm) Percent Corro- Chan Co 0- HaO tn 9 1 I ston I" x siiiii Hydro- 83%,; Change 2" x Change cam? g (lb./s gfg (lb./s

strip tin/yr. strip (ta/yr. (gms.) (3111s.)

120 4s 0.057 -0.0176 0.232 +.000e .008 120 4a 0.1 -o.02sa -0.376 +.0004 .005

EXAMPLE 5 A series of experiments was carried out to determine the efiect of polymerization reaction temperature. The details of these experiments are shown in Table 111. These data show that, over the entire range of temperature from -40 up to 60 C., substantially the same good results were obtained with regard to resin yield, softening po1nt,l1odine number values, intrinsic viscosity and Gardner co or. e

TABLE III Efiect of polymerization temperature Feed Naphtha v i 2 I I I I Catalyst 1%.0! 3C mesh AlOh-Powder Reaction Temp., 0..... I I 40' 0 4511111 Catalyst Removal OHQOH Precipitation Water and Caustic Was g:

andFiltraton Resin Yield, Wt. Percent [1 Feed 9 29. 6 26.6 26. 5 18 29. 8 32. 5 30. 9 Resin Properties: 7

Soft. Pt. 92 82 89 V 90 91 e o 116 92 104410. 104410 104-110 104-110, Intrinsic Viscosity.. 0. 042 0.037 7 Color Light amber 2 3 2 3 1 Nnphfha 1 2 Composition, Wt. Percent:

Benzene 20 ii). 6 To1uena 9 4. 2v 0: Aromatics.. 1. 1 Parafdns 1. 1 Dinlpflne 14.5 V 15 Ol fin 65.5 60.2 Distillation, Wt. Percent overhead;

I. B. P.38 C 17 3. 9 3870 O. 22 39. 9 70430 C. 59 52. 7 130 G. 2, 3. v5

9 Stripped to a. bottoms temperature of 260-270 C. at 2-5 mm. Hg. 3 5 ml. of 0.2 N Wijs Reagent per 0.04-0.055 g. resin.

EXAMPLE 7 A. number of different methods for catalyst removal were also tested to determine: the. effectof this variable on the propertiesv of the resin produced. The details, of this study are shown in Table V. In general, the particular method used for recovering: resin was foundnot 40 to be of great consequence with regard to resin quality. Methods tested included the precipitation of the Al,C la by methyl alcohol. followed by filtration, and alcohol, caustic EXAMPLE 6 Experiments were carried out to study the efiect of 35 type and concentration of catalyst on the. quality of resin produced. The details. of these experiments are shown in Table IV. It. was found. that AlBra dissolved in n-hexane, solid AlCls including powdered AlCla, an ethyl chloride solution of M013, and an n-hexane slurry of AlCla can be used quite satisfactorily to give high quality resins. Variations in catalyst concentrations of from 0.75% up to 2.0% based on the hydrocarbon feed can be employed. or water washing.

TABLE IV V Efiect of catalyst type and concentration Feed Naphtha 1 w 3 I I Catal st AlBr; A1013. A101; A101,. A101;

W t. Percent on Hydrocarbon Feed. 1.0 0.75-.- 1.0..-. 2.0..-. 0;53 l' 1.1-... Method of Cat. Addn Soln. in n- So1id Solid. So11d-. 0135C Solu- Hexane tion Reaction Temp., O 20 20 20-.- 20 20.....] 20 35.

OH OH Pr r inifafirn & Filtration. Hot. Water Washing 28.2.-- 29.6--- 35.2...- 22.8-... 26.0- 255 29.4. Resin Properties:

Soft. Pt. 0 92. 83 86 89 l Naphtha. 1 3.

Composition, wt. percent:

Benzene V l U 20 29.1 Toluene it 6.8 Ca aromatics 1 1 Paraifins. 1 1 Dinlafinq 14, 5 4 Olefins 65. 5 49. l

Distillation, wt. (percent overhead:

I. B. P.38 1 7 8 38-70 C 22 25 70l30 G 59 64- C 2 3 I Stripped to a bottoms temperature of 260270 O. at 2-5 mm. Hg. 3 6 ml. oi 0.2 N Wijs Reagent per 0.04-0.055 g. resin.

TABLE ,V

Effect of catalyst recovery method- (Y 1r:

Feed Naphtha 1 Catalyst Wt. percent on Hydrocarbon Feed-.-

Method of Cat. Addn Reaction Temp, C 35. Catalyst Removal Resin Yield 7 20 35. Caustic Wash- Hot Water Washing g. 26.2 25.5 29.4.

0.120 Light to mednm amber V V V V V 1 Naphtha Composition, wt. percent:

Benzene Tnlmm a Aromatics Olefins Distillation, wt. Cpercent; overhead:

1 Stripped to a bottoms temperature of zoo-210 O. at 2-5 mm. Hg. ml. of 0.2 N Wljs Reagent per 0.04-0.055 g; resin.

What is claimed is: 1. In a process for the preparation of improved petroleum resins the combination which comprises isolating a steamed cracked hydrocarbon petroleum fraction boiling between about more than C.'-to less than 140 C.,

said fraction being substantially below C9, heating the steam cracked fraction to' a' temperature sufficient to dimerize substantially all cyclodienes, stripping the resulting admixture to a temperature sufficient to separate an overhead product from the dimerized cyclodienes, recovering as the overhead product a stream boiling between about more than 20 C. to less than 140 C. and having the following composition; 7

I Weight percent said composition being substantially free of cyclodienes,

and polymerizing the stream in the presence of an aluminum halide catalyst at a temperature of about -40 C. to +70 C. and recovering the resin formed thereby.

2. In a process for the preparation of improved petroleum resins, the combination which comprises isolating a steam cracked petroleum fraction boiling between about 20 C. and 140 C., said fraction being substantially below C9, heating the fraction to. a temperature of about 90 C.-140 0., whereby to dimerize substantially all the cyclodienes, stripping the resulting admixture to a temperature of not more than about 450 F. but sufiicient to separate an overhead product from the cyclodienes, recovering as the overhead product a stream boiling between about more than 20 C. to'less than 140? C and the following composition:

- 4,981,708- Thomas; 2,039,363

said stream being substantially free from cyclodienes, and polymerizing the stream in the presence of an aluminum chloride catalyst at a temperature between about 40 C. to C. and recovering the resin formed therebyQ 3. In a process for the preparation of a petroleum resin, the improvement which comprises isolating a steamcracked petroleum fraction boiling'between about 20 to 140 C., heating the fraction to a temperature sulficient to dimerize substantially all cyclodienes, removing the dimerized cyclodienes to leave a mixture comprising about 11 to 25 weight percent diolefins, said mixture having the following distillation analysis:

Weight percent I. B. P. to 38 C 0-30 38-70" C 25-50 70-130 C -15 .1 30-1 ;0" C 0- 5 polymerizing said substantially cyclodiene-free mixture in the presence of an aluminum halide catalyst at atemperature of about -40 C. to +70 C; and recovering the resin formed thereby.

4. Process according to claim? in 'which'the catalyst is aluminum chloride.

5. Process according to.claim 3 in which the catalyst is aluminum bromide.

6. Process according to claim 3 in which o f the cyclodiene-free mixture isz:

' Weight'percent Benzene r Y 15-30 Toluene 3-10 C8 aromatics A Diolefins 11-25 sass...assass ns star; was

- UNITED. STATES RAT NT I Thomas -May 5, 1936 2,521,022 Rowland Sept. 5, 1950 the analysis 

1. IN A PROCESS FOR THE PREPARATION OF IMPROVED PETROLEUM RESINS THE COMBINATION WHICH COMPRISES ISOLATING A STEAMED CRACKED HYDROCARBON PETROLEUM FRACTION BOILING BETWEEN ABOUT MORE THAN 20* C. TO LESS THAN 140* C., SAID FRACTION BEING SUBSTANTIALLY BELOW C9, HEATING THE STEAM CRACKED FRACTION TO A TEMPERATURE SUFFICIENT TO 